WO2000038524A1 - Agents antibacteriens a l'aluminosilicate - Google Patents

Agents antibacteriens a l'aluminosilicate Download PDF

Info

Publication number
WO2000038524A1
WO2000038524A1 PCT/JP1999/007244 JP9907244W WO0038524A1 WO 2000038524 A1 WO2000038524 A1 WO 2000038524A1 JP 9907244 W JP9907244 W JP 9907244W WO 0038524 A1 WO0038524 A1 WO 0038524A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminosilicate particles
group
antibacterial agent
aluminosilicate
particles
Prior art date
Application number
PCT/JP1999/007244
Other languages
English (en)
Japanese (ja)
Inventor
Mikio Sakaguchi
Takanori Kodera
Original Assignee
Kao Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corporation filed Critical Kao Corporation
Priority to JP2000590488A priority Critical patent/JP3292726B2/ja
Publication of WO2000038524A1 publication Critical patent/WO2000038524A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

Definitions

  • the present invention relates to an antibacterial agent comprising aluminosilicate particles having a novel particle form carrying a metal (sometimes referred to as an aluminosilicate antibacterial agent).
  • aluminosilicate antibacterial agent comprising aluminosilicate particles having a novel particle form carrying a metal (sometimes referred to as an aluminosilicate antibacterial agent).
  • Zeolite particles carrying an antibacterial metal are inexpensive and highly stable, so they are widely applied to polymers and fibers as antibacterial agents.
  • the antibacterial agent disclosed in Japanese Patent Publication No. 63-260810 A zeolite composition is disclosed.
  • zeolite particles exhibit a smooth, dice-like angular shape with a smooth surface due to the cubic habit of the crystal system, and are therefore kneaded into polymers and fibers, and coated on these surfaces together with a binder.
  • the binding to the polymer or the fiber is not sufficient, and the strength of the polymer or the fiber may be deteriorated.
  • the surface area of the zeolite particles alone or exposed on the surface of polymers, fibers, etc. is small, so that the antibacterial effect is insufficient.
  • the exposed surface area is not a specific surface area due to gas adsorption or the like, but is a surface that is preferably in contact with bacteria, in other words, a geometric surface area. Disclosure of the invention
  • An object of the present invention is to provide an aluminosilicate antibacterial agent having excellent antibacterial properties and filling properties.
  • the gist of the present invention is:
  • M is Na and Z or K
  • R is Na
  • A is from the group consisting of C0 3, S O4, NO3, OH and C 1
  • a is 1 to 6
  • b is 2 to 8
  • c is 2 to 12
  • d is 0 to 4 (excluding 0)
  • m is 1 to 2
  • n is 1 to 3
  • y indicates 0 to 32
  • Aluminosilicate particles having a composition represented by the following formula and having any one of a needle shape, a plate shape, and a columnar shape include at least one selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg, and Ce.
  • Antibacterial agent consisting of aluminosilicate particles carrying metal
  • M is Na and Z or K
  • R is Na, K
  • A is CO 3, S0 4, NOs, from the group consisting of OH and C 1
  • a! Is 0 to 1 (except 1), a and + a 2 are 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4, m is 1 to 2, and n is 1 -3 and y indicate 0-32.
  • a 2 H 20 indicates structural water present in the crystal
  • yH 20 indicates crystal water.
  • Aluminosilicate particles having a composition represented by the following formula and having any one of a needle shape, a plate shape, and a columnar shape include at least one selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg, and Ce.
  • An antimicrobial agent comprising aluminosilicate particles carrying a metal, and
  • M is Na and Roh or K
  • R is Na
  • a is 1 to 6
  • b is 2 to 8
  • c is 2 to 12
  • d is 0 to 4 (excluding 0)
  • m is 1 to 2
  • n is 1 to 3
  • y indicates 0 to 32)
  • Aluminum having a composition represented by the formula: needle-like, plate-like, or columnar Nosilicide particles are protonated, and then antibacterial consisting of metal-supported aluminosilicate particles that carry one or more metals selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg and Ce.
  • a method for producing an antibacterial agent BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a view showing the crystal morphology of the raw material aluminosilicate particles obtained in Example 7.
  • FIG. 2 shows an X-ray diffraction pattern 5 of the raw material aluminosilicate particles obtained in Example 7.
  • FIG. 3 is a view showing a crystal form of the antibacterial agent particles obtained in Example 9.
  • FIG. 4 is an X-ray diffraction pattern of the antibacterial agent particles obtained in Example 9. BEST MODE FOR CARRYING OUT THE INVENTION
  • Aluminosilicate gate particles used as a raw material in the present invention have the formula (1): aM 2 0 ⁇ b A 12 0 3 ⁇ c S i 0 2 - d RmAn ⁇ y H 2 0
  • M is Na and / or K
  • R is Na, K
  • A is C_ ⁇ 3, S0 4, N0 3, from ⁇ _H and C 1
  • a is 1 to 6
  • b is 2 to 8
  • c is 2 to 12
  • d is 0 to 4 (excluding 0)
  • m is 1 to 2
  • n is 1 ⁇ 3
  • y indicates 0 ⁇ 32
  • the antibacterial agent of the present invention has one major feature in using aluminosilicate particles having the above composition and having the above form. By using such aluminosilicate particles, it has excellent antibacterial properties and also has good filling properties for polymers, fibers The effect that an excellent antibacterial agent can be obtained is exhibited.
  • M is preferably Na.
  • aM 2 ⁇ is, ai 'Naz O' az ' Ks OC
  • a + a 2' represented by a).
  • R is preferably N a
  • A is preferably C_ ⁇ 3 or N_ ⁇ 3.
  • the aluminosilicate particles used in the present invention have a needle-like, plate-like, or columnar shape.
  • the needle-like form refers to a form having a thickness of 50 O nm or less and an aspect ratio of 2.0 or more to the thickness
  • the plate-like form refers to a thickness. Is 300 nm or less, and the plate diameter is 2.0 or more in terms of the aspect ratio with respect to the thickness.
  • the columnar shape means that the thickness is 50 nm or more and the length is long. It means that the aspect ratio with respect to the thickness is 1.0 or more and less than 2.0.
  • Such aluminosilicate particles can be obtained as an aggregate of needle-like crystals, plate-like crystals or columnar crystals depending on the production conditions.
  • the aluminosilicate particles are preferably those in which the above-mentioned crystals are aggregated to form a spherical, tetrapod-like, or massive aggregate, and these secondary aggregates may be used.
  • the aluminosilicate particles are a spherical aggregate
  • the “main X-ray diffraction peak” refers to the strongest peak or a peak showing a diffraction intensity of 20% or more of the strongest diffraction peak intensity.
  • JCPDS Joint Commiteon Powder Diffraction Standards
  • JCPDS Joint Commiteon Powder Diffraction Standards
  • aluminosilicate particles JCPDS (Joint Commiteon Powder Diffraction Standards) No. 20-379, 20-743, 25-776, 25-149, 2 5-1 5 0 0, 3 0-1 1 70, 3 1-1 272, 34-1 76, 3 5-4 79, 35-6 53, 3 8-5 1 3, 3 8-5 1
  • Those having at least one type of force-clinite-like X-ray diffraction pattern selected from the group consisting of 4, 38—5 15 and 45-1373 are preferred.
  • the average particle size of the aluminosilicate particles used in the present invention is preferably from 0.1 to 500 m, more preferably from 1 to 100 m.
  • equation (2) when the specified aluminosilicate particles are used as a raw material of an antibacterial agent and the antibacterial agent is kneaded into a plastic, it may react with an antioxidant and change color. Therefore, from the viewpoint of preventing such discoloration, equation (2):
  • M is Na and or K
  • R is Na, K
  • C one or more of the Bareru selected from the group consisting of a and Mg, bees (0 3, 30 4, 1 ⁇ 0 3, one or more Bareru selected from the group consisting of ⁇ _H and C 1, a, from 0 to 1 (where , 1), a, + a 2 is 1 to 6, b is 2 to 8, c is 2 to 12, d is 0 to 4, m is 1 to 2, n is 1 to 3, y is 0 To 32.]
  • an aluminosilicate particle (hereinafter, sometimes referred to as an aluminosilicate particle (A)) having a composition represented by the following formula and having any one of a needle shape, a plate shape, and a column shape as an antibacterial agent.
  • a 2 H 2 ⁇ denotes structural water present in the crystals of the aluminosilicate particles (A), and such water component is a so-called immobile water which is not released by heating. is there.
  • yH 20 indicates crystallization water present in the crystals of the aluminosilicate particles (A), and such water components are released by heating at 600 at 1 hour.
  • the aluminosilicate particles (A) represented by the formula (2) are the aluminosilicate particles represented by the formula (1) [The aluminosilicate particles represented by the formula (1) are referred to as raw material aluminosilicate particles. May be obtained by performing a protonation treatment described below. In the aluminosilicate particles used as raw materials, d is a value other than 0. In the aluminosilicate particles (A), d may be 0.
  • the antimicrobial agent in which a metal is supported on such aluminosilicate particles (A) is a raw material before protonation treatment. Its crystallinity is lower than that of aluminosilicate particles.
  • the crystallinity of the antibacterial agent is 1% or more and less than 100% as compared with the raw material aluminosilicate particles before the protonation treatment, preferably. Is 1 to 50%, more preferably 1 to 20%.
  • the crystallinity of the aluminosilicate particles is lower than 1%, it becomes difficult to carry the amount of metal necessary for the expression of antibacterial properties. Therefore, the crystallinity is preferably 1% or more.
  • the crystallinity can be determined by X-ray diffraction, and refers to the ratio of the highest diffraction intensity of the antimicrobial agent at the same peak to the highest diffraction intensity of the aluminosilicate particles as a raw material.
  • the crystallinity of the antibacterial agent can be adjusted to a desired range by the degree of the protonation treatment.
  • aluminosilicate Ichito particles used in the present invention include, but are not limited especially, for example, an alumina raw material and silica raw material C_ ⁇ 3 2 -, S_ ⁇ 4 2 -, N 0 3 -, C
  • the reaction may be carried out in an alkaline solution in the presence of 1-or the like.
  • the alumina raw material include aluminum oxide, aluminum hydroxide, and sodium aluminate.
  • the silica raw material include gay sand, silica stone, water glass, and sodium gayate.
  • a raw material for both the alumina raw material and the silica raw material for example, clay minerals such as kaolin, montmorillonite, bentonite, myriki, talc, and aluminosilicate minerals such as mullite may be used. Good.
  • C_ ⁇ 3 2 - The raw materials, carbon dioxide, sodium carbonate, potassium carbonate, sodium potassium, calcium carbonate, magnesium carbonate and the like, S_ ⁇ 4 2 -
  • the raw material for NO 3 include sodium sulfate, potassium sulfate, and potassium sodium sulfate.
  • the NO 3 ⁇ material include nitric acid, sodium nitrate, and potassium nitrate.
  • the C 1 ⁇ material include sodium chloride and chloride. Potassium and the like.
  • Examples of the alkali of the alkaline solution include oxides such as sodium oxide and potassium oxide; hydroxides such as sodium hydroxide and hydroxylated lime; carbonates such as sodium carbonate, carbonated lime and sodium carbonate; Sodium bicarbonate, bicarbonate such as hydrogen bicarbonate, etc. can be used. If necessary, oxides such as calcium oxide and magnesium oxide; hydroxides such as calcium hydroxide and magnesium hydroxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; calcium hydrogen carbonate and magnesium hydrogen carbonate And the like may be used.
  • the aluminosilicate particles used in the present invention can be obtained by blending and mixing the above various compounds at a predetermined ratio.
  • the mixing ratio is appropriately determined depending on the desired composition of the obtained aluminosilicate particles.
  • the solid content concentration of the aluminosilicate particles represented by the above composition during the reaction is desirably 0.1 to 50% by weight.
  • the reaction temperature when producing aluminosilicate particles increases the degree of crystallinity of the aluminosilicate particles, stabilizes the morphology of the aluminosilicate particles, and reduces the chemical and pressure resistance load on the reaction vessel.
  • the temperature is preferably 15 to 300 ° C, more preferably 60 to 150 ° C, and further preferably 80 to 130 ° C.
  • the reaction time is preferably at least 2 hours, more preferably at least 8 hours, from the viewpoint of completely performing the crystallization reaction.
  • the aluminosilicate particles obtained by such a method are excellent in sorption properties and dispersibility, and have the property of increasing the mechanical strength of the filling material when used as a filler.
  • powders are suitable because of their high dispersibility.
  • a metal is supported on the aluminosilicate particles.
  • the metal used in the present invention is at least one selected from the group consisting of Ag, Cu, Fe, Zn, Ca, Mg and Ce. Since these are antibacterial metals, they are supported. Aluminosilicate particles are useful as antibacterial agents.
  • antibacterial refers to fungi and bacteria, and refers to the property of killing or inhibiting the growth of these bacteria.
  • Examples of a method for supporting a metal include an ion exchange method and a method for depositing fine metal particles.
  • the ion exchange method include a method in which aluminosilicate particles are dispersed in a solution of a metal salt, ion-exchanged, filtered, washed, dried, and, if necessary, heat-treated.
  • the method for depositing fine metal particles there is a method in which aluminosilicate particles are dispersed in a solution of a metal salt, and fine metal particles are precipitated on the surfaces of the aluminosilicate particles using a precipitant such as an acid or an alkali.
  • the amount of metal carried in the antibacterial agent should be 0.1 to 10% by weight in terms of the total amount of metals such as Ag, Cu, Fe, Zn, Ca, Mg, and Ce from the viewpoint of antibacterial properties and economy. And more preferably 0.5 to 5% by weight.
  • the amount of metal carried in the antibacterial agent is measured by X-ray fluorescence. It is to be noted that the crystallization of the obtained antibacterial agent does not substantially change simply by supporting the metal on the aluminosilicate particles as a raw material.
  • proton treatment proton exchange by reacting in H 2 S_ ⁇ 4, HC 1, HN0 3, NH 4 N 0 gradually acidic aqueous solution containing 3 or the like aluminosilicate gates particles, or once Then, a method of heating or heating as necessary is used. Further, after the support, heat treatment may be performed at 100 to 800 ° C. if necessary. Such a protonation treatment is performed before or after the metal is supported on the aluminosilicate particles. You can do it when you let it.
  • a specific protonation method is as follows.
  • the aluminosilicate particles are dispersed in ion-exchanged water so as to have a solid concentration of 1 to 30% by weight.
  • the pH of the slurry at this time is between 8 and 13.
  • the acid is slowly added to the slurry while stirring.
  • it is preferable to perform the acid treatment so that the pH of the slurry is 2 to 7, preferably 3 to 5.
  • the pH of the slurry during the acid treatment is preferably within this range. .
  • the antibacterial agent of the present invention obtained by the above-described method is not only excellent in antibacterial properties but also has a complex surface, so that it is also excellent in filling properties and used in powder. It may be used as a mixture with other inorganic powders, organic powders, metal powders and the like, and may be used as a molded product if necessary. Specific applications include additives for various detergents, fillers for paper, plastics, fibers, fabrics, and building materials, pigments for cosmetics, and water treatment agents.
  • the antibacterial agent of the present invention and the anti-discoloration agent and stabilizer may be simultaneously added, or may be adhered to and coated on the particle surface.
  • discoloration inhibitors or stabilizers include metal oxides such as zinc oxide, phosphate, hydrotalcites, magnesium oxide, calcium oxide, titanium oxide, calcium stearate, phenolic, sulfuric, and phosphorus-based materials.
  • Antioxidants, ultraviolet absorbers and the like will be described in more detail with reference to Examples.
  • the produced aluminosilicate particles were washed, filtered, and dried to obtain powder of the aluminosilicate particles.
  • the obtained aluminosilicate particles had a form in which needle-like crystals were aggregated.
  • the powder of the obtained aluminosilicate particles was subjected to X-ray diffraction using an X-ray diffractometer (RAD-C, CuK, manufactured by Rigaku Corporation). It had a strong diffraction peak at 69 nm, which corresponded to J CPDS No. 38-513.
  • the composition of the aluminosilicate gates particles been filed schematically 3Na 2 0 ⁇ 3 A 1 2 ⁇ 3 ⁇ 6 S i 0 2 ⁇ NaN_ ⁇ 3 ⁇ 4 H 2 0.
  • Example 2 77 g of the obtained powder of aluminosilicate particles was added to a solution of 3.38 g of silver nitrate dissolved in 1000 Om1 of ion-exchanged water, and dispersed at 100 ° C for 1 hour to ion-exchange Ag. After that, the mixture was filtered and washed to obtain Antibacterial Agent 1.
  • the obtained antibacterial agent 1 had a spherical shape in which needle-like crystals were aggregated, and contained 2.38% by weight of Ag.
  • the amount of metal such as Ag in the antibacterial agent was measured by X-ray fluorescence.
  • Example 2 50 g of the aluminosilicate powder used in Example 1 was added to ion-exchanged water to which 75 g of 1N hydrochloric acid had been added, dispersed at 100 ° C. for 1 hour, and subjected to protonation treatment. Ag was ion-exchanged in the same manner as in Example 1 to obtain Antibacterial Agent 2.
  • the obtained antibacterial agent 2 showed a spherical morphology in which needle-like crystals similar to the antibacterial agent 1 were aggregated, had a crystallinity of 76%, and supported 2.48% by weight of Ag.
  • Example 2 In a solution prepared by dissolving 16 g of the aluminosilicate particles obtained in Example 1 in 63 ml of silver nitrate and 7.279 g of zinc nitrate hexahydrate in 160 ml of deionized water. The mixture was dispersed at 100 ° C. for 2 hours, ion-exchanged Ag and Zn, and then filtered and washed to obtain antibacterial agent 3.
  • the obtained antimicrobial agent 3 is the same needle as antimicrobial agent 1. It exhibited a spherical morphology of aggregates of crystalline crystals, and 2.49% by weight of Ag and 7.7% by weight of Zn were supported.
  • Example 2 16 g of the aluminosilicate particles obtained in Example 1 was dissolved in a solution obtained by dissolving 2.683 g of silver nitrate 63 and calcium nitrate tetrahydrate in 1.600 ml of ion-exchanged water. The mixture was added and dispersed at 100 ° C. for 2 hours to ion-exchange Ag and Ca, followed by filtration and washing to obtain antibacterial agent 4.
  • the obtained antibacterial agent 4 exhibited a spherical morphology in which needle-like crystals were aggregated like the antibacterial agent 1, and contained 2.38% by weight of Ag and 1.9% by weight of Ca.
  • Example 2 16 g of the aluminosilicate particles obtained in Example 1 were mixed with 0.63 g of silver nitrate, 2.9 13 g of magnesium nitrate hexahydrate and 14.08 g of ammonium nitrate in deionized water. It was added to a solution dissolved in 160 ml, dispersed at 100 ° C. for 2 hours, ion-exchanged Ag and Mg, and then filtered and washed to obtain antibacterial agent 5. The obtained antibacterial agent 5 exhibited a spherical morphology in which needle-like crystals were aggregated, as in antibacterial agent 1, and contained 2.38% by weight of Ag and 7.7% by weight of ⁇ .
  • a powder of 77 g of the aluminosilicate particles obtained in Example 1 was dissolved in 3.000 g of ion-exchanged water with 3.38 g of silver nitrate and 3.4.1 g of cerium nitrate hexahydrate.
  • the solution was added to the solution, dispersed at 100 ° C. for 1 hour, ion-exchanged Ag and Ce, and then filtered and washed to obtain antibacterial agent 6.
  • the obtained antibacterial agent 6 exhibited a spherical morphology in which needle-like crystals were aggregated as in antibacterial agent 1, and contained 2.5% by weight of Ag and 2.8% by weight of Ce.
  • aluminosilicate particles was obtained in the same manner as in Example 1. The obtained aluminosilicide particles were composed of columnar and needle-like crystals which were aggregated into tetrapods.
  • the composition of the aluminosilicate particles was approximately 3Na 2 0 '3A l 2 0 3 ⁇ 7Si 0 2 -2NaN0 3 -. 4 were are H 2 ⁇ the S EM photograph of the obtained aluminosilicate Ichito particles
  • Figure 1 shows the X-ray diffraction pattern in Figure 2.
  • antibacterial agent 7 showed a form in which columnar and needle-like crystals aggregated and developed into a tetrapod-like form, and contained 2.49% by weight of Ag.
  • Antibacterial agent 2 obtained in Example 2 was further heat-treated at 600 ° C. for 5 hours to obtain antibacterial agent 8.
  • the obtained antimicrobial agent 8 had the same particle morphology and Ag carrying amount as antimicrobial agent 1.
  • Example 7 After 100 g of the raw material aluminosilicate particles obtained in Example 7 were dispersed in 900 g of ion-exchanged water and the temperature was raised to 100 ° C, lmo 1 Z1 aqueous nitric acid solution was added to 1 m 1 / 95 Om 1 was added dropwise at a rate of minutes. The pH of the solution at the end of the dropwise addition was 3.2. The solid content was separated by filtration, washed, and ion-exchanged water containing 58 g of silver nitrate dissolved therein 900 g g, and dispersed at 100 ° C. for 1 hour to carry out Ag ion exchange, followed by filtration and washing to obtain antibacterial agent 9.
  • the crystallinity of the obtained antibacterial agent 9 was 36%, and octane was carried in an amount of 0.91% by weight.
  • Approximate composition of an antimicrobial agent, excluding the A g was 3 ⁇ 2 0 ⁇ 3 A 12 0 3 ⁇ 7 S i 0 2 ⁇ 0. 2NaN_ ⁇ 3 ⁇ 4 ⁇ 2 ⁇ .
  • Fig. 3 shows a SEM photograph of the obtained antibacterial agent
  • Fig. 4 shows its X-ray diffraction pattern.
  • the crystallinity of the antibacterial agent was determined by comparing the maximum diffraction intensity in the X-ray diffraction pattern of the raw material aluminosilicate particles obtained in Example 7 shown in FIG. 2 with the antibacterial agent obtained in this example shown in FIG. It was calculated as the ratio of the highest diffraction intensity, which is the same corresponding peak in the X-ray diffraction pattern of the agent.
  • the crystallinity of the antibacterial agent in other examples was calculated in the same manner.
  • Example 7 After 100 g of the aluminosilicate particles obtained in Example 7 were dispersed in 900 g of ion-exchanged water and heated to 100 ° C, 300 ml of lmo 1/1 nitric acid aqueous solution was added at a rate of lm 1 / min. It was dropped. The pH of the solution at the end of the dropwise addition was 4.9. After the solids were separated by filtration and washed, 1.58 g of silver nitrate was added to 900 g of ion-exchanged water in which they had been dissolved, dispersed at 100 ° C for 1 hour, and subjected to Ag ion exchange, followed by filtration and washing. Thus, an antibacterial agent 10 was obtained.
  • the obtained antimicrobial agent 10 had a crystallinity of 45% and was loaded by 98% by weight of ⁇ t.
  • Approximate composition of an antimicrobial agent, excluding the A g was 3H 2 0 ⁇ 3 A 12 0 3 ⁇ 7 S i 0 2 ⁇ 0. 2NaN_ ⁇ 3 ⁇ 4 ⁇ 2 ⁇ .
  • the antibacterial properties of the antibacterial agents 1 to 10 obtained in Examples 1 to 10 were evaluated.
  • Staphylococcus aureus IFO12732
  • Antibacterial agents were suspended and dispersed in an agar medium, and the respective minimum inhibitory concentrations (MIC) after 24 hours at 37 ° C. was evaluated.
  • MIC minimum inhibitory concentrations
  • Table 1 As a comparative example, a conventional zeolite carrying an antibacterial metal (Ag, carrying amount: 2.0% by weight) was used. In the table, ⁇ indicates that the growth of the fungus was inhibited, and X indicates that the fungus had grown.
  • the antimicrobial agents 1 to 10 obtained in Examples 1 to 10 all had a lower MIC than the conventional antimicrobial metal-supported zeolite used in Comparative Examples. It is small and has excellent antibacterial properties. Industrial applicability
  • the aluminosilicate antibacterial agent of the present invention has excellent antibacterial properties, has an aggregated form such as a sphere, and has a large surface area, and therefore has excellent filling properties. And fillers for paper, plastics, fibers, building materials, etc., pigments for cosmetics, and water treatment agents.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Paper (AREA)

Abstract

L'invention concerne des agents anti-bactériens à l'aluminosilicate, présentant d'excellentes propriétés anti-bactériennes et de tassement. Ces agents anti-bactériens consistent en particules d'aluminosilicate présentant la composition suivante: aM2O.bAl2O3.cSiO2.dRmAn.yH2O (M représentant Na et/ou K; R représentant un ou plusieurs éléments choisis dans le groupe constitué de Na, K, Ca et Mg; A représentant un ou plusieurs éléments choisis dans le groupe constitué de CO3, SO4, NO3, OH et Cl; a vaut 1 à 6; b vaut 2 à 8; c vaut 2 à 12; d vaut 0 à 4 (0 étant exclu); m vaut 1 à 2; n vaut 1 à 3; et y vaut 0 à 32). Lesdits agents se présentent sous forme d'aiguilles, de plaques ou de colonnes, et portent un ou plusieurs métaux choisis dans le groupe formé par Ag, Cu, Fe, Zn, Ca, Mg et Ce.
PCT/JP1999/007244 1998-12-25 1999-12-24 Agents antibacteriens a l'aluminosilicate WO2000038524A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2000590488A JP3292726B2 (ja) 1998-12-25 1999-12-24 アルミノシリケート抗菌剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/371076 1998-12-25
JP37107698 1998-12-25

Publications (1)

Publication Number Publication Date
WO2000038524A1 true WO2000038524A1 (fr) 2000-07-06

Family

ID=18498103

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/007244 WO2000038524A1 (fr) 1998-12-25 1999-12-24 Agents antibacteriens a l'aluminosilicate

Country Status (3)

Country Link
JP (1) JP3292726B2 (fr)
TW (1) TW592638B (fr)
WO (1) WO2000038524A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002244339A (ja) * 2001-02-21 2002-08-30 Tomoegawa Paper Co Ltd 静電荷像現像用トナー
JP2002284517A (ja) * 2001-03-26 2002-10-03 Kao Corp アルミノシリケート粒子
JP2003012403A (ja) * 2001-06-25 2003-01-15 Earth Chem Corp Ltd 害虫防除用毒餌剤
JP2004244789A (ja) * 2003-01-21 2004-09-02 Kao Corp 消臭抗菌繊維製品
WO2005014059A1 (fr) * 2003-08-08 2005-02-17 Kao Corporation Deodorant
JP2005232654A (ja) * 2004-02-23 2005-09-02 Kao Corp 消臭抗菌繊維製品
JP2006191966A (ja) * 2005-01-11 2006-07-27 Kao Corp 吸収性物品
JP2006307404A (ja) * 2005-03-30 2006-11-09 Kao Corp 消臭抗菌繊維製品
JP2014218486A (ja) * 2013-05-10 2014-11-20 公立大学法人大阪市立大学 抗菌性消臭剤および抗菌性消臭剤の製造方法
CN114276582A (zh) * 2020-09-27 2022-04-05 合肥杰事杰新材料股份有限公司 一种抗菌剂及其制备方法、含有该抗菌剂的抗菌组合物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60100505A (ja) * 1983-05-06 1985-06-04 デンツプライ　インタ−ナシヨナル　インコ−ポレ−テツド 重合性材料用酸素バリヤ−層
EP0190903A2 (fr) * 1985-02-04 1986-08-13 Exxon Research And Engineering Company Composition de zéolite cristalline de structure semblable à la cancrinite et son procédé de préparation
EP0270129A2 (fr) * 1986-12-05 1988-06-08 Shinagawa Fuel Co., Ltd. Zéolithe antibiotique
WO1999023033A1 (fr) * 1997-10-31 1999-05-14 Kao Corporation Aluminosilicate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60100505A (ja) * 1983-05-06 1985-06-04 デンツプライ　インタ−ナシヨナル　インコ−ポレ−テツド 重合性材料用酸素バリヤ−層
EP0190903A2 (fr) * 1985-02-04 1986-08-13 Exxon Research And Engineering Company Composition de zéolite cristalline de structure semblable à la cancrinite et son procédé de préparation
EP0270129A2 (fr) * 1986-12-05 1988-06-08 Shinagawa Fuel Co., Ltd. Zéolithe antibiotique
WO1999023033A1 (fr) * 1997-10-31 1999-05-14 Kao Corporation Aluminosilicate

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002244339A (ja) * 2001-02-21 2002-08-30 Tomoegawa Paper Co Ltd 静電荷像現像用トナー
JP2002284517A (ja) * 2001-03-26 2002-10-03 Kao Corp アルミノシリケート粒子
JP4614562B2 (ja) * 2001-03-26 2011-01-19 花王株式会社 アルミノシリケート粒子
JP2003012403A (ja) * 2001-06-25 2003-01-15 Earth Chem Corp Ltd 害虫防除用毒餌剤
JP4731741B2 (ja) * 2001-06-25 2011-07-27 アース製薬株式会社 害虫防除用毒餌剤
JP2004244789A (ja) * 2003-01-21 2004-09-02 Kao Corp 消臭抗菌繊維製品
JP4526271B2 (ja) * 2003-01-21 2010-08-18 花王株式会社 吸収性物品
US7662354B2 (en) 2003-08-08 2010-02-16 Kao Corporation Deodorant
JP4721899B2 (ja) * 2003-08-08 2011-07-13 花王株式会社 消臭剤
WO2005014059A1 (fr) * 2003-08-08 2005-02-17 Kao Corporation Deodorant
JP4526278B2 (ja) * 2004-02-23 2010-08-18 花王株式会社 消臭抗菌繊維製品
JP2005232654A (ja) * 2004-02-23 2005-09-02 Kao Corp 消臭抗菌繊維製品
JP2006191966A (ja) * 2005-01-11 2006-07-27 Kao Corp 吸収性物品
JP4651392B2 (ja) * 2005-01-11 2011-03-16 花王株式会社 吸収性物品
JP2006307404A (ja) * 2005-03-30 2006-11-09 Kao Corp 消臭抗菌繊維製品
JP2014218486A (ja) * 2013-05-10 2014-11-20 公立大学法人大阪市立大学 抗菌性消臭剤および抗菌性消臭剤の製造方法
CN114276582A (zh) * 2020-09-27 2022-04-05 合肥杰事杰新材料股份有限公司 一种抗菌剂及其制备方法、含有该抗菌剂的抗菌组合物

Also Published As

Publication number Publication date
JP3292726B2 (ja) 2002-06-17
TW592638B (en) 2004-06-21

Similar Documents

Publication Publication Date Title
JP5317293B2 (ja) 陰イオン交換性層状複水酸化物の製造方法
JP6951022B2 (ja) 成長速度が遅くアスペクト比が低い水酸化マグネシウム粒子およびその製造方法
KR20130081293A (ko) 수산화 마그네슘 미립자, 산화 마그네슘 미립자 및 이들의 제조방법
WO2000038524A1 (fr) Agents antibacteriens a l'aluminosilicate
JP2615274B2 (ja) 抗菌性炭酸カルシウム粉体
WO2009096597A1 (fr) Matière adsorbante sélective et procédé pour la production de celle-ci
JP4338470B2 (ja) ハイドロタルサイト粒子及びその製造方法
JP2005272170A (ja) 金属水酸化物／ゼオライト複合体及びその製造法
JP3977151B2 (ja) 消臭剤
ES2229105T3 (es) Elementos conformados in situ que contienen arcilla anionica cristalina.
CN109502656B (zh) 一种球状Co(Ⅱ)Co(Ⅲ)类水滑石材料及其制备方法
CA2870652A1 (fr) Compositions chimiques antimicrobiennes
KR100929402B1 (ko) 항균 다공성 비드 및 그 제조방법
CA2105593C (fr) Tobermorite renfermant du metal argent
JP2006281068A (ja) 吸着剤
JPH09241019A (ja) 炭酸型ハイドロカルマイトの合成方法
JP2000007326A (ja) 紡錘状乃至球状アルカリアルミニウム硫酸塩水酸化物、その製造法及び樹脂配合剤
JP4863192B2 (ja) 高い陰イオン交換能を有する炭酸汚染し難い安定性に優れた層状複水酸化物とその合成方法
JP2016107257A (ja) 吸着剤及びその製造方法
JP4015212B2 (ja) イオン交換剤
JP2000264626A (ja) カルシウム−アルミニウム系層状複水酸化物の製造方法
JPWO2020040270A1 (ja) 層状複水酸化物結晶、アニオン吸着剤および該層状複水酸化物結晶の製造方法
JPH06191854A (ja) 水中の遊離塩素の分解剤
CA2343145A1 (fr) Sel polybasique composite modifie par zinc, procede de production de ce sel, et utilisation
WO2021039584A1 (fr) Cristal d'hydroxyde double stratifié, adsorbant d'anions et méthode de production de cristal d'hydroxyde double stratifié

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref country code: JP

Ref document number: 2000 590488

Kind code of ref document: A

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase